JP7451428B2 - Azole silane compound - Google Patents

Description

The present invention relates to certain azole silane compounds, oligomers thereof, mixtures comprising said compounds and/or said oligomers, and respective storage and use solutions. Furthermore, the present invention relates to a method for synthesizing said particular azole silane compound and to the use of said use solution as a surface treatment solution.

Azole silane compounds are frequently utilized in the production of electronic components, in particular in surface treatment solutions, for example for the treatment of metal surfaces and the surfaces of organic materials in preparation for further processing steps.

US Patent Application Publication No. 2016/0368935 relates to azole silane compounds, surface treatment solutions using the azole silane compounds, surface treatment methods and uses thereof.

JP2018-016865A discloses a triazole surface treatment agent containing a silane compound.

Paper "Corrosion protection of copper with 3-glycidoxypropyltrimethoxysilane-based sol-gel coating through 3-amino-5-mercapto-1,2,4-triazole doping", Journal of Research on Chemical Intermediates, Vol. 42, No. 2, 1315- Page 1328, 2015 discloses a study on the corrosion protection of copper in neutral media by the formation of a sol-gel coating on the copper surface. This suggests that a 3-amino-5-mercapto-1,2,4-triazole-doped 3-glydidoxypropyltrimethoxysilane-based sol-gel coating on copper forms thiolate bonds to the copper. Disclose.

JP-A-06-279461 refers to a surface treatment agent for improving rust prevention on metal surfaces, in particular a surface treatment agent for copper foil used in copper-clad laminates for printed circuits. ing. The drug is an azole silane obtained by reacting 1H-1,2,4-triazole-3-thiol with 3-glycidoxypropyltrimethoxysilane at 80-200°C.

The paper ``Recovery of rhodium-containing catalysts by silica-based chelating ion ex-changers containing N and S donor atoms,'' Journal of Inorganica Chimica Acta 315 (2001), pp. 183-190, was prepared before immobilization on silica. Disclosed is 4-amino-3-methyl-1,2,4-triazole-5-thione attached to a bifunctional spacer (3-glycidoxypropyl)trimethoxysilane.

Due to the structural diversity of azole silane compounds, most such compounds must be manufactured on demand and are typically not readily available as standard commercial products. Therefore, there is a need for a simple and efficient synthesis method.

Typically, azole silane compounds readily polymerize in the presence of water by forming silicon-oxygen-silicon bonds. This is often undesirable immediately after compound synthesis. Although polymerization may be desirable for the end use, it is usually necessary to synthesize it de novo in a way that on the one hand prevents too much and/or premature polymerization of the monomer, but on the other hand allows for further processing of the compound. There is a need to solubilize such compounds in solvents. Furthermore, it is desirable to have a sufficiently high concentration of the respective azole silane compounds in such solvents in order to economically transport them to another manufacturing site. In practice, the solubility of known azole silane compounds in typically utilized/desired solvents is often not sufficient.

Additionally, the synthesis of azole silane compounds often involves educts containing halides such as chloride, bromide, and iodide. During synthesis, such halides are often released and contaminate the resulting synthetic product. This typically means that additional purification steps are required to remove the halides and their respective salts. However, such additional steps significantly increase the risk of water contamination leading to premature polymerization. Moreover, such purification steps often have a negative impact on the overall yield of the final azole silane compound. If acceptable, such azole silane compounds are not purified, so that the halides and their respective salts remain with the azole silane compounds. However, in many applications it is completely undesirable to work with azole silane compounds with halides. In other cases, it is undesirable to utilize azole silane compounds with variable amounts of halides, even though halides are generally accepted.

US Patent Application Publication No. 2016/0368935 Japanese Patent Application Publication No. 2018-016865 Japanese Patent Application Publication No. 06-279461

"Corrosion protection of copper with 3-glycidoxypropyltrimethoxysilane-based sol-gel coating through 3-amino-5-mercapto-1,2,4-triazole doping", Journal of Research on Chemical Intermediates, Vol. 42, No. 2, 1315-1328 Page, 2015 "Recovery of rhodium-containing catalysts by silica-based chelating ion ex-changers containing N and S donor atoms", Journal of Inorganica Chimica Acta 315 (2001), pp. 183-190

Therefore, a first object of the present invention is to provide azole silane compounds with increased solubility in suitable solvents, based on the above-mentioned problems. A second object of the present invention is to provide a synthetic method that is simple and efficient, in particular that does not release halides and their respective salts so that additional purification steps can be avoided. be.

The first objective mentioned above is that formula (I)

[In the formula,
X represents _NH2 , NH( _NH2 ), NH(NHU), SH, _SCH3 , _OCH3 , NHU, or SU,
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents H or C1-C5 alkyl]
This problem is solved by azole silane compounds.

The second purpose is to use formula (I)

[In the formula,
X represents _NH2 , NH( _NH2 ), NH(NHU), SH, _SCH3 , _OCH3 , NHU, or SU,
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl]
A method for synthesizing an azole silane compound, comprising:
(i) Formula (III)

[In the formula,
X represents _NH2 , NH( _NH2 ), SH, _SCH3 , or _OCH3 ,
Y represents NH, N(NH ₂ ), or S]
a step of preparing an azole compound;
(ii) Formula (IV)

[In formula (IV),
R represents (CH ₂ -CH ₂ -O) _m -Z, and independently,
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl,
n is an integer in the range 1 to 12]
a step of preparing a silane compound;
(iii) reacting said azole compound with said silane compound in a solvent to result in said compound of formula (I);
(iv) Optionally, the compound of formula (I) obtained in step (iii) is hydrolyzed so that at least one of R is m=0 and Z=H (CH ₂ -CH ₂ - O) _m -Z.

Our own experiments have shown that the synthetic method described above yields azole silane compounds with improved solubility and stability in certain solvents. Furthermore, the above synthetic method utilizes an educt that does not have a halogen atom. Therefore, no halide ions are released into the respective solvent during the synthesis. This is highly desirable since specific amounts of each halide can be added so that the total concentration is precisely known even if halide ions are required in further applications.

The invention particularly relates to certain azole silane compounds as defined above. Azolesilane compounds of the invention are often preferred in which Y represents NH, N(NH ₂ ), or N(NHU), preferably NH and N(NH ₂ ), most preferably NH. In other cases, azolesilane compounds according to the invention in which Y represents S are preferred. Among the two, Y containing nitrogen is preferable to the case where Y is S.

Azoles according to the invention, wherein X represents _NH2 , NH( _NH2 ), SH, _SCH3 or _OCH3 , preferably _NH2 , NH( _NH2 ), SH or _SCH3 , more preferably _NH2 Silane compounds are preferred.

In U, n is an integer in the range of 1 to 8, preferably in the range of 2 to 6, more preferably in the range of 3 to 4, most preferably n is 3, the azole of the invention Silane compounds are preferred.

Very preferred are formulas (I-I) or (I-II)

[In the formula,
R is independently (CH ₂ -CH ₂ -O) _m -Z;
independently,
m is 0, 1, or 2, preferably 0 or 2;
Z is H, CH ₃ , CH ₂ -CH ₃ , (CH ₂ ) ₂ -CH ₃ or (CH ₂ ) ₃ -CH ₃ , preferably H, CH ₃ or (CH ₂ ) ₃ -CH ₃ represents,
B is independently selected from the group consisting of H and _NH2 , preferably B is H]
The azole silane compound of the present invention is a compound of

Highly preferred are compounds of formula (I-II).

In the context of the present invention, the term "independently" (or similar expressions) in combination with certain variables means that the selected feature for such variable in the first compound is (e.g., variable B in (I-I) and (I-II)), and when one compound contains at least two of the same variables ( For example in the variables B) in (I-II), this signifies that they are selected independently of each other and can therefore be different. For example, in compounds of formula (I-II), B is independently selected from B in compounds of formula (I-I). Therefore, both B's can be different. Furthermore, in compounds of formula (I-II), the B attached to the ring azole nitrogen is independently selected from the B in the external amine group. Thus, again, both B's may be different in compounds of formula (I-II). This principle applies equally to other "independently" terms.

More preferred is formula (Ia) or (Ib)

[In the formula,
R is independently (CH ₂ -CH ₂ -O) _m -Z;
independently,
m is 0, 1, or 2, preferably 0 or 2;
Z is H, _CH3 , _CH2 - _CH3 , ( _CH2 ) ₂ - _CH3 , or ( _CH2 ) ₃ - _CH3 , preferably H, _CH3 , or ( _CH2 ) ₃ - _CH3 , most preferably represents H and ( _CH2 ) ₃ - _CH3 ]
The azole silane compound of the present invention is a compound of

Most preferred are azolesilane compounds of the invention, wherein Y comprises nitrogen, each of which is preferably a compound of formula (Ib) and (I-II), respectively, as defined above. be.

The invention also relates to oligomers of the azole silane compounds of the invention. Therefore, the present invention provides that, in the presence of water, formula (I)

[In the formula,
X represents H, CH ₃ , NH ₂ , NH(NH ₂ ), NH(NHU), SH, SCH ₃ , OCH ₃ , NHU, or SU;
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents H or C1-C5 alkyl]
azole silane compounds (preferably compounds of formula (I) described as particularly preferred throughout this specification) with each other such that the azole silane oligomer contains at least one silicon-oxygen-silicon moiety. Related to azole silane oligomers obtained by This reaction can also be called oligomerization.

The oligomerization described above requires at least a small amount of water for hydrolysis to form at least some OH groups on the various silicon atoms. Preferably, the azole silane oligomers are obtained by reacting the azole silane compounds with each other in the presence of at least 2% by weight of water, based on the total weight of the respective reaction composition.

In the context of the present invention, the term "azole silane oligomer" includes a combination of at least two monomers, ie at least two azole silane compounds of the invention, reacted with each other. Additionally, the term includes up to 3, 4, 5, 6, 7, 8, 9, and 10 monomers. Preferred are from the group consisting of azolesilane dimer, azolesilane trimer, azolesilane tetramer, azolesilane pentamer, azolesilane hexamer, azolesilane heptamer, and azolesilane octamer. Selected azole silane oligomers of the present invention. More preferred are azolesilane oligomers of the invention selected from the group consisting of azolesilane dimers, azolesilane trimers, and azolesilane tetramers. The latter alternatively means that azole silane oligomers of the invention containing one, two or three silicon-oxygen-silicon moieties, respectively, are preferred.

Based on the azole silane compounds of the invention, a wide variety of oligomers of the invention can be formed. Therefore, the oligomers of the present invention are best and appropriately described by their interactions with each other.

In the context of the present invention, the term "at least" in combination with a particular value stands for (and is interchangeable with) this value or a value exceeding this value. For example, "at least one silicon-oxygen-silicon moiety" above refers to (and is interchangeable with) "one or more silicon-oxygen-silicon moieties." Most preferably, "at least one" stands for (and is interchangeable with) "one, two, three or more than three."

Most preferred is formula (II)

[In the formula,
R independently represents (CH ₂ -CH ₂ -O) _m -Z,
m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2;
Z represents H or C1-C5 alkyl,
k is 1, 2 or 3, preferably 1 or 2,
M is independently the formula (IIa)

(In formula (IIa),
X is H, CH ₃ , NH ₂ , NH(NH ₂ ), SH, SCH ₃ or OCH ₃ , preferably CH ₃ , NH ₂ , NH(NH ₂ ), SH, SCH ₃ or OCH ₃ , or more preferably represents _NH2 , NH( _NH2 ), SH or _SCH3 , most preferably _NH2 ;
Y represents NH, N(NH ₂ ), or S, preferably NH;
n represents an integer in the range 1 to 12, preferably in the range 1 to 8, more preferably in the range 2 to 6, even more preferably in the range 3 to 4, most preferably n is 3 )
]
The oligomer of the present invention is a compound of

In the above part of formula (IIa), the dashed line represents a covalent bond that connects the entire part to the silicon atom shown in formula (II).

Only in a few cases are further preferred azole silane oligomers according to the invention, in which k is an integer in the range from 1 to 7, preferably from 1 to 5. However, most preferably k is 1, 2 or 3, preferably 1 or 2.

Preferably, the oligomers of the invention are homo-oligomers. This means that preferably identical monomers are combined with each other to form oligomers.

It is alternatively preferred that in the oligomers of the invention at least all moieties that do not form a silicon-oxygen-silicon skeleton (i.e. the azole moiety and the ether moiety linking the azole moiety to the silicon atom) are It is the same. In such cases, M is preferably not independently defined.

The azole silane compounds of the present invention and the azole silane oligomers of the present invention may exist as a mixture. Alternatively, more than one compound or more than one oligomer may be present as a mixture. Typically, organic solvents promote solubility. Therefore, the present invention also provides
(a) - one or more azole silane compounds according to the invention (as described throughout the specification, preferably as preferred); and/or
- one or more azole silane oligomers according to the invention (as described throughout the specification, preferably as preferred),
(b)- relates to mixtures comprising, preferably consisting of, one or more than one organic solvent;

Preferably, the mixture of the invention is substantially free of, preferably free of, halide ions.

In the context of the present invention, the term "substantially free" of an object (e.g. a compound, substance, etc.) means that said object is either completely absent or in a very small and unobtrusive amount. only present and does not affect the intended purpose of the invention. For example, such objects may be added or utilized unintentionally, for example as unavoidable impurities. "Substantially free" means 0 (zero) ppm to 50 ppm, preferably 0 ppm to 25 ppm, more preferably 0 ppm to 10 ppm, even more preferably Preferably it represents 0 ppm to 5 ppm, most preferably 0 ppm to 1 ppm. 0 ppm represents no content of the respective target, which is most preferred. This principle applies equally to other aspects of the invention, such as the storage solutions of the invention (see herein below) and the use solutions of the invention (also see herein below).

Preference is given to mixtures according to the invention, in which the total amount of all the azole silane compounds according to the invention and the oligomers according to the invention together is from 5% by weight, based on the total weight of the mixture. 30% by weight, preferably 8% to 26% by weight, more preferably 12% to 24% by weight, even more preferably 15% to 21% by weight. most preferably in the range of 17% to 20% by weight. Preferably, the mixture is substantially free of, and preferably free of, other azole silane compounds and azole silane oligomers, respectively, that are not according to the invention.

Highly preferred are mixtures according to the invention that are substantially free of water, preferably water-free. Preference is therefore given to mixtures according to the invention in which the one or more azole silane compounds according to the invention are substantially free of, preferably free from -SiOH groups.

Preferably, the one or more organic solvents are acetone, 1,3-dioxolane, acetonitrile, 1,4-dioxane, methanol, ethanol, 1-propanol, 2-propanol, t-butanol, propanol. 2-en-1-ol, ethyl lactate, ethylene glycol monomethyl ether acetate, N,N-dimethylformamide, 2-butoxyethanol, di(propylene glycol) methyl ether, tetrahydrofurfuryl alcohol, N-methyl-2-pyrrolidone, 2-(2-methoxyethoxy)ethanol, gamma-butyrolactone, ethylene glycol, propylene glycol, dipropylene glycol, epsilon-caprolactone, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, tetrahydrothiophene-1-oxide, diethylene glycol monobutyl ether acetate, carbonic acid A mixture of the present invention comprising a solvent selected from the group consisting of propylene, sulfolane, glycerol, and mixtures thereof.

Very preferably, the one or more organic solvents are methanol, ethanol, 1-propanol, 2-propanol, t-butanol, di(propylene glycol) methyl ether, ethylene glycol, propylene glycol, dipropylene A mixture of the present invention comprising a solvent selected from the group consisting of glycol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

In a few cases, it is highly preferred that the one or more organic solvents are preferably from the group consisting of di(propylene glycol) methyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof. A mixture according to the invention comprising a solvent selected from the group consisting of selected glycol ethers.

In the context of the present invention, the inventive mixtures defined above are preferably the direct result of the respective synthetic procedure, such as the inventive synthetic method (see below for further details).

Preference is furthermore given to mixtures according to the invention (as described throughout the specification, preferably described as preferred), which contain all azole silane compounds according to the invention (as described throughout the specification, preferably preferred). preferred) and all azole silane oligomers according to the invention (described throughout the specification, preferably described as preferred) of all compounds containing at least one silicon atom in said mixture. A mixture comprising at least 51 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, most preferably at least 80 mol%, even more preferably at least 90 mol%. The foregoing preferably applies equally to the alkaline storage solutions of the invention (see herein below) and the aqueous use solutions of the invention (see herein below), respectively.

The present invention also provides
(a) - one or more azole silane compounds according to the invention (as described throughout the specification, preferably as preferred), and
- optionally one or more azole silane oligomers according to the invention (as described throughout the specification, preferably as preferred),
(b)- water;
(c)- Relates to alkaline storage solutions containing one or more water-miscible organic solvents, provided that the pH is 9 or higher.

Preferably, the alkaline storage solution of the present invention is substantially free of, and preferably free of, halide ions. It is preferred that halide ions are present only in a few cases by intentional addition of halide ions, preferably by intentional addition of chloride ions.

Preference is given to storage solutions according to the invention, in which all the azole silane compounds according to the invention (as described throughout the specification, preferably described as preferred) and all the azole silanes according to the invention are present. The total amount of oligomers (as described throughout this specification, preferably preferred) together ranges from 0.5% to 15% by weight, preferably 0.8%, relative to the total weight of the alkaline storage solution. % to 12% by weight, more preferably 1.0% to 10% by weight, even more preferably 1.5% to 8% by weight, most preferably 2.2% to 6% by weight. % by weight of the stock solution.

The storage solution contains water. Preference is given to storage solutions according to the invention, in which water in the alkaline storage solution ranges from 10% to 80% by weight, preferably from 15% to 78% by weight, relative to the total weight of the alkaline storage solution. % by weight, more preferably in the range from 20% to 76% by weight, even more preferably in the range from 33% to 74% by weight, most preferably in the range from 38.6% to 70% by weight. A stock solution is present.

Besides water, the alkaline storage solution contains one or more water-miscible organic solvents. Such organic solvents provide the necessary solubility of the respective azole silane compounds and their oligomers, especially when they are present in relatively high concentrations (e.g. up to and about 15% by weight, see hereinabove). Promote in case. Preference is therefore given to storage solutions according to the invention, in which the one or more water-miscible organic solvents are present in an amount of 5% to 89.5% by weight, based on the total weight of the alkaline storage solution. most preferably in the range of 10% to 84.2% by weight, more preferably in the range 14% to 79% by weight, even more preferably in the range 18% to 65.5% by weight. is a stock solution present in a total amount ranging from 24% to 59% by weight.

In many cases, alkaline storage solutions of the invention are preferred in which the total mass of water is less than the total mass of all water-miscible organic solvents.

As mentioned above, the storage solution is alkaline. In the context of the present invention, this means that the pH is 9 or higher. Preferred are storage solutions of the invention, wherein the solution has a pH of 9.6 or higher, preferably the pH ranges from 10.4 to 13, more preferably the pH ranges from 10.5 to 12.4, most preferably the pH ranges from 10.5 to 12.4. is a stock solution with a pH ranging from 10.6 to 11.9. When the pH is significantly lower than pH 9, the solubility of azole silane compounds and their oligomers decreases to the point where undesirable precipitation occurs. Acidic pH is not suitable for storage purposes since precipitation has often been observed at relatively high concentrations of the silaneazole compounds of the present invention and their corresponding oligomers at such pH. Conversely, if the pH is significantly higher than 13, undesirable phase separation and decomposition of the azole silane compounds are frequently observed.

In the context of the present invention, pH is referenced to a temperature of 20°C.

In the alkaline storage solution of the present invention, an alkaline pH is obtained, preferably by utilizing at least one alkaline hydroxide, most preferably by utilizing sodium hydroxide.

The alkaline pH not only allows for relatively high concentrations of the azole silane compounds and their respective oligomers in the storage solution. The alkaline pH further strongly maintains the azole silane compounds of the present invention in their monomeric state, significantly reducing the formation of the azole silane oligomers of the present invention. However, when such an oligomer is formed in the alkaline storage solution of the present invention, it is typically rapidly hydrolyzed to form its monomeric form due to the alkaline pH. This is desirable in the storage solutions of the present invention.

Preference is given to storage solutions according to the invention, in which the total mass of all the azolesilane compounds according to the invention is greater than the total mass of all the azolesilane oligomers according to the invention. .

In some cases, for at least 80% by weight, preferably for at least 90% by weight, most preferably for at least 95% by weight of the total weight of all inventive azole silane compounds, Z is H and m is 0 Preference is given to storage solutions of the invention in which: This means that in the storage solution the azole silane compound is primarily present in its hydrolyzed form containing SiOH groups.

The alkaline storage solutions described above are particularly suitable for transporting and/or storing one or more azole silane compounds of the invention. However, in order to utilize the compounds as surface treatment solutions, for example in the production of electronic components, the respective use solutions are preferred. The invention therefore further provides an aqueous use solution having a pH in the range of 4.8 to 8.0, comprising:
(a) - one or more azole silane compounds according to the invention (as described throughout the specification, preferably as preferred); and/or
- one or more azole silane oligomers according to the invention (as described throughout the specification, preferably as preferred),
(b)- at least 51% by weight of water, based on the total weight of the solution used;
(c)- containing one or more water-miscible organic solvents, in said use solution containing all azole silane compounds according to the invention (as described throughout the specification, preferably as preferred); ) and all the azole silane oligomers according to the invention (as described throughout the specification, preferably as preferred) together are less than or equal to 5% by weight, based on the total weight of the aqueous use solution. , relating to aqueous use solutions.

Particular preference is given to said aqueous use solutions according to the invention with the proviso that they contain at least one azole silane oligomer according to the invention (as described throughout the specification, preferably preferred). This is particularly preferred for freshly prepared use solutions.

The above term "5% by mass or less" does not include 0% by mass. This means that said total amount is always >0% by weight, preferably at least 0.1% by weight.

Preference is given to use solutions according to the invention, in which all the azole silane compounds according to the invention (as described throughout the specification, preferably described as preferred) and all the azole silane compounds according to the invention are preferred. Preferably, the total amount of azole silane oligomers (as described throughout this specification, preferably as preferred) is in the range 0.1% to 4% by weight, based on the total weight of the aqueous use solution. is in the range of 0.2% to 3% by weight, more preferably in the range of 0.3% to 2.2% by weight, even more preferably in the range of 0.4% to 2.0% by weight, most preferably 0.5% by weight. ~1.8% by weight of the working solution.

Our own experiments have shown that the individual presence of one or more azole silane compounds according to the invention and one or more azole silane oligomers according to the invention can vary over time. It is shown. In a freshly prepared use solution, typically the total mass of the azole silane compounds of the present invention is greater than the total mass of the azole silane oligomers of the present invention. However, over time when using a working solution, the total mass of the azole silane oligomers increases rapidly, potentially to the point where the total mass of the azole silane oligomers is greater than the total mass of the azole silane compounds. Furthermore, the handling of the use solution of the invention also affects the total mass of each of the compounds and oligomers. For example, significant pumping out of use solution during utilization and corresponding replenishment of fresh use solution typically leads to steady state conditions in terms of azole silane compound versus azole silane oligomer.

Most preferably, the use solution of the invention comprises:
- one or more azole silane compounds according to the invention (as described throughout the specification, preferably as preferred), and
- one or more than one azole silane oligomer according to the invention (as described throughout the specification, preferably as preferred); Therefore, respective use solutions comprising at least one compound and at least one oligomer are most preferred.

The use solution of the invention has a pH in the range 4.8 to 8.0. Preferred are use solutions of the invention whose pH is in the range 5.6 to 7.9, more preferably in the range 5.8 to 7.7, most preferably in the range 6.5 to 7.5. A pH in the range of 4.8 to 8.0 supports oligomerization of the azole silane compounds of the present invention, at least to some extent, which is desirable (although it is undesirable in storage solutions). Furthermore, a total amount of all azolesilane compounds according to the invention and all azolesilane oligomers according to the invention of up to 5% by weight, based on the total weight of the aqueous use solution, and the result that said use solution is primarily an aqueous solution. As a result, a sufficiently stable working solution is obtained. This means that precipitation can be significantly avoided at such total amounts and at such pH in an aqueous environment. For example, if the pH is significantly lower than pH 4.8 or significantly higher than pH 8.0, undesirable and strong precipitation is often observed.

As already mentioned, the use solution of the invention is an aqueous solution. Preference is given to use solutions according to the invention, in which water is present in a total amount in the range from 56% to 88% by weight, preferably from 60% by weight, based on the total weight of the aqueous use solution. The use solution is present in a total amount ranging from 84.8% by weight, more preferably from 65% to 82.2% by weight.

One or more water-miscible organic solvents are present in order to sufficiently solubilize the azole silane compounds of the invention and the azole silane oligomers of the invention in the aqueous use solutions of the invention. Preference is given to use solutions according to the invention, in which the one or more water-miscible organic solvents comprise from 6% to 44% by weight, based on the total weight of the aqueous use solution. preferably in a total amount in the range 8% to 43.9% by weight, more preferably in a total amount in the range 13% to 39.7% by weight, most preferably in a total amount in the range 16% to 34.5% by weight. Use solution present in total amount.

As mentioned above, in the context of the present invention, the azole silane compounds of the present invention and the azole silane oligomers of the present invention are initially free of halides. This means, on the one hand, that the compounds and oligomers are free of halide atoms themselves, since no educts containing halogen atoms are utilized, and on the other hand, that the halide ions are present in the immediate synthetic environment. means that it does not exist. However, in some cases it is preferred that the aqueous use solutions of the invention contain precisely defined amounts of halide ions. Therefore, in some cases, the aqueous use solution of the present invention comprises:
(d)- It is preferred that it further contains a halide ion, preferably a chloride ion.

However, in other cases the aqueous use solutions of the present invention are substantially free, preferably free, of chloride ions, more preferably substantially free, preferably free of halide ions. preferably does not include this.

One or more water-miscible organic solvents are present in both the alkaline storage solution of the invention and the aqueous use solution of the invention. Preferably, the one or more water-miscible organic solvents are selected from the group consisting of C1-C4 alcohols, glycol ethers, and mixtures thereof, preferably
- C1-C3 alcohol,
- HO-(CH ₂ -CH ₂ -O) _m -Z
[In the formula,
m is 1, 2, 3, or 4, preferably 1 or 2;
Z represents C1-C5 alkyl, preferably C3-C5 alkyl],
and mixtures thereof, more preferably
Even more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.
selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof;
an alkaline storage solution according to the invention (as described throughout the specification, preferably preferred), or an aqueous use solution according to the invention (as described throughout the specification, preferably preferred), comprising a water-miscible organic solvent; preferred).

The water-miscible organic solvents defined above apply equally to the synthetic method of the invention (see herein below).

In each case, glycol ethers are preferred over alcohols. Glycol ethers typically provide improved stabilization compared to the alcohols. Additionally, alcohols generally exhibit low flash points compared to glycol ethers, making them potentially dangerous in terms of flame hazard. A relatively high flash point is usually desirable to prevent ignition. Therefore, glycol ethers typically provide the desired solubility, stability, and safety. This principle preferably applies equally to the mixtures according to the invention, the alkaline storage solutions according to the invention and the synthetic methods according to the invention (see herein below).

Preference is given to alkaline storage solutions according to the invention (as described throughout the specification, preferably described as preferred) or aqueous use solutions according to the invention (as described throughout the specification, preferably as preferred). ), all azole silane compounds according to the invention (as described throughout the specification, preferably described as preferred) and all azole silane oligomers according to the invention (as described throughout the specification, preferably described as preferred). more preferably represents at least 70% by weight, preferably at least 80% by weight of the total weight of all azole silane compounds and oligomers in each of said storage solution and said use solution. is an alkaline storage solution or an aqueous use solution comprising at least 90% by weight, even more preferably at least 93% by weight, most preferably at least 95% by weight, even more preferably at least 98% by weight. . Most preferably, no other azole silane compounds or oligomers other than those according to the invention are present. This also means that the absolute total amount of azole silane compounds and azole silane oligomers (as just defined hereinabove) taken together is the same as that of the alkaline storage solutions of the present invention and the azole silane oligomers of the present invention. It is also meant to be applied very preferably with the proviso that it is not present in each of the aqueous use solutions.

Furthermore, preference is given to alkaline storage solutions according to the invention (as described throughout the specification, preferably preferred) or aqueous use solutions according to the invention (as described throughout the specification, preferably as preferred). described), all azole silane compounds according to the invention (as described throughout the specification, preferably described as preferred) and all azole silane oligomers according to the invention (as described throughout the specification). , preferably described as preferred) accounts for at least 51 mol%, preferably at least 60 mol% of all compounds containing at least one silicon atom in each of said storage solution and said use solution. Preferably it is an alkaline storage solution, or an aqueous use solution, comprising at least 70 mol%, most preferably at least 80 mol%, even more preferably at least 90 mol%.

The present invention also provides formula (I)

[In the formula,
X represents _NH2 , NH( _NH2 ), NH(NHU), SH, _SCH3 , _OCH3 , NHU, or SU,
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl]
A method for synthesizing an azole silane compound, comprising:
(i) Formula (III)

[In the formula,
X represents _NH2 , NH( _NH2 ), SH, _SCH3 , or _OCH3 ,
Y represents NH, N(NH ₂ ), or S]
a step of preparing an azole compound;
(ii) Formula (IV)

[In formula (IV),
R represents (CH ₂ -CH ₂ -O) _m -Z, and independently,
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl,
n is an integer in the range 1 to 12]
a step of preparing a silane compound;
(iii) reacting said azole compound with said silane compound in a solvent so as to result in a compound as defined above of formula (I);
(iv) Optionally, the compound of formula (I) obtained in step (iii) is hydrolyzed so that at least one of R is m=0 and Z=H (CH ₂ -CH ₂ - O) _m -Z.

What has been said above regarding the azole silane compounds of the invention (which are preferably described as preferred) preferably applies analogously to the synthetic methods of the invention, for example regarding the highly preferred azole silane compounds of the invention.

Step (iv) is optional and comprises the presence of at least some water to hydrolyze the compound obtained in step (iii) of the process of the invention. Preferably, such water is added in an additional step, such as step (iv), after step (iii). If such a compound is desired (m=0 and Z=H), step (iv) is not optional.

Very preferably, in step (iii), the solvent comprises an organic solvent, more preferably one or more organic solvents, most preferably one or more water-miscible solvents. The synthesis method of the present invention is an organic solvent.

Often, in step (iii), the solvent is selected from the group consisting of C1-C4 alcohols, glycol ethers, and mixtures thereof, preferably
- C1-C3 alcohol,
-HO-( _CH2 - _CH2 -O) _m -Z
[In the formula,
m is 1, 2, 3, or 4, preferably 1 or 2,
Z represents C1-C5 alkyl, preferably C3-C5 alkyl],
and mixtures thereof, more preferably
Even more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.
selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof;
Preferred are synthetic methods of the invention in which one or more than one solvent is used.

Generally, glycol ethers are preferred over the alcohols defined above (see herein above for reasons). Therefore, each synthetic method of the invention is preferred.

Preference is given to the synthetic process of the invention (especially as described above), in which the solvent in step (iii) is substantially free of water, preferably free of water.

Preferably, the solvent in step (iii) is one or more organic solvents, and after step (iii) of the process of the invention, a mixture according to the invention is obtained (mixtures are described herein). (see above). What has been said above regarding the mixtures according to the invention applies equally to the synthetic methods according to the invention.

More preferably, the total molar ratio of compounds of formula (III) to compounds of formula (IV) is in the range 1:0.85 to 1:1.3, preferably in the range 1:0.90 to 1:1.25. The synthesis method of the present invention preferably ranges from 1:0.95 to 1:1.2, most preferably from 1:1.0 to 1:1.15. If the total molar ratio is significantly higher than 1:1.3, the synthesis product is not stable enough. If the total molar ratio is significantly lower than 1:0.85, too many unreacted educts will be present in the synthesis product, which is undesirable since the desired species are azole and azole silane compounds containing silane moieties. . This principle preferably applies equally to the mixtures according to the invention, the alkaline storage solutions according to the invention and the aqueous use solutions according to the invention.

Preferred is the method of synthesis according to the invention, wherein in step (iii) the temperature is in the range 50°C to 90°C, preferably in the range 60°C to 85°C.

Preference is given to the synthetic method of the invention, in which in step (i) the azole compound of formula (III) is provided as a suspension. This means that the azole compound of formula (III) is preferably suspended in at least one solvent such that said azole compound and said at least one solvent form said suspension. do. For that, it is preferred that the at least one solvent is one or more organic solvents, preferably one or more water-miscible organic solvents. Very preferably, the at least one solvent utilized to form said suspension is the same as the solvent utilized in step (iii). Most preferably, the azole compound of formula (III) is selected from the group consisting of C1-C4 alcohols, glycol ethers, and mixtures thereof, preferably
- C1-C3 alcohol,
- HO-(CH ₂ -CH ₂ -O) _m -Z
[In the formula,
m is 1, 2, 3, or 4, preferably 1 or 2,
Z represents C1-C5 alkyl, preferably C3-C5 alkyl],
and mixtures thereof, more preferably
Most preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.
selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof;
Suspended in one or more solvents.

Preferred is the synthesis method of the invention, wherein in step (iii) the reaction is carried out for 1 hour to 48 hours, preferably 3 hours to 24 hours, more preferably 5 hours to 20 hours.

The invention also relates to the above-mentioned aqueous use solutions of the invention (as described throughout the specification, preferably as preferred), preferably as surface treatment solutions for treating metal surfaces and/or surfaces of organic materials. ). Preferably, both metal surfaces and organic materials are included in the manufacture of electronic components.

The invention is further illustrated by the following non-limiting examples.

A) Synthesis of azole silane compound of formula (I):
1) Synthesis of azole silane compound of formula (Ia):

In the first step, 3.68 g (27.1 mmol) of 5-amino-1,3,4-thiadiazole-2-thiol (an azole compound of formula (III), where X represents NH ₂ and Y represents S) was suspended in 70 ml of methanol to obtain an azole suspension.

In the second step, 6.59 g (27.1 mmol) of 3-glycidoxypropyltrimethoxysilane (silane compound of formula (IV), where R represents CH ₃ and n is 3) is dissolved in 20 ml of methanol. The solution prepared by this was added to the azole suspension. As a result, a reaction suspension was obtained.

In the third step, the reaction suspension was heated to reflux (temperature approximately 65° C.) for 18 hours. During that time, the suspension became a clear solution, indicating that the azole compound was completely used up. The solvent (methanol) was then removed and approximately 10 g (100% yield) of a yellow, highly viscous material was obtained as a product which was primarily an azole silane compound of formula (Ia). The product thus obtained was free of halides and was utilized without further purification.

¹ H NMR: (400 MHz, DMSO-d ₆ ) δ 7.24 (s, 2H), 5.22 (d, J = 5.4 Hz, 1H), 3.81 (dq, J = 7.1, 5.2 Hz, 1H), 3.51 - 3.43 (m, 8H), 3.41 - 3.30 (m, 5H), 3.30 - 3.13 (m, 2H), 3.05 (dd, J = 13.1, 7.1 Hz, 1H), 1.59 - 1.44 (m, 2H), 0.68 - 0.51 (m, 2H)

ESI-MS: m/z:369.08(100.0%), 370.09(11.9%), 371.08(9.0%)

Both NMR and ESI-MS confirm the presence of an azole silane compound of formula (Ia). The theoretical molar mass is 369 g/mol.

2) Synthesis of azole silane compound of formula (Ib):

In the first step, 3.36 g (28.4 mmol) of 5-amino-4H-1,2,4-triazole-3-thiol (an azole of formula (III), where X represents NH ₂ and Y represents NH) Compound) was suspended in 70 ml of methanol to obtain an azole suspension.

In the second step, 6.91 g (28.4 mmol) of 3-glycidoxypropyltrimethoxysilane (silane compound of formula (IV), where R represents CH ₃ and n is 3) is dissolved in 20 ml of methanol. The solution prepared by this was added to the azole suspension. As a result, a reaction suspension was obtained.

In the third step, the reaction suspension was heated to reflux (temperature approximately 65° C.) for 18 hours. During that time, the suspension became a clear solution, indicating that the azole compound was completely used up. The solvent (methanol) was then removed and approximately 10 g (100% yield) of a yellow, highly viscous material was obtained as a product which was primarily an azole silane compound of formula (Ib). The product thus obtained was free of halides and was utilized without further purification.

¹ H NMR: (400 MHz, DMSO-d ₆ ) δ 6.03 (s, 2H), 5.33 - 5.08 (m, 1H), 3.87 - 3.75 (m, 1H), 3.54 - 3.25 (m, 13H), 3.22 - 3.08 (m, 1H), 2.97 (dd, J = 13.3, 7.0 Hz, 1H), 1.55 (dddd, J = 12.7, 11.1, 6.6, 3.5 Hz, 2H), 0.67 - 0.50 (m, 2H)

ESI-MS: m/z:352.12(100.0%), 353.13(11.9%)

Both NMR and ESI-MS confirm the presence of an azole silane compound of formula (Ib). The theoretical molar mass is 352 g/mol.
The above synthesis of the azole silane compound of formula (Ib) can be carried out using various molar ratios ( molar rations).

3) Synthesis of azole silane compound of formula (Ib) in DEGBE:
In the first step, 3.36 g (28.4 mmol) of 5-amino-4H-1,2,4-triazole-3-thiol (an azole of formula (III), where X represents NH ₂ and Y represents NH) Compound) was suspended in 35 ml of diethylene glycol monobutyl ether (DEGBE) to obtain an azole suspension.

In the second step, 6.91 g (28.4 mmol) of 3-glycidoxypropyltrimethoxysilane (silane compound of formula (IV), where R represents CH ₃ and n is 3) is dissolved in 10 ml of DEGBE. The solution prepared by this was added to the azole suspension. As a result, a reaction suspension was obtained.

In the third step, the reaction suspension was heated to 80° C. for 15 hours. During that time, the suspension became a clear solution, indicating that the azole compound was completely used up. Afterwards, a concentration of the reaction product in DEGBE of approximately 18% by weight was obtained. The product thus obtained was completely free of halides and was utilized without further purification. Additionally, no solvent changes or removals, such as those described above in Examples 1 and 2, were necessary.

ESI-MS confirms the formation of a compound containing three methoxy groups bonded to a silicon atom. In addition, compounds containing one, two, or three DEGBE moieties in place of each methoxy group have also been identified.

B) Synthesis of reference azole silane compounds (not according to the invention):
For comparison, a reference azole silane compound of formula (X) was synthesized.

The reference compound of formula (X) is disclosed in US Patent Application Publication No. 2016/0368935 as compound (1-8). The synthesis of this reference compound is based on Examples 1-8 in US Patent Application Publication No. 2016/0368935 and was performed as follows:

In the first step, 5-amino-1,3,4-thiadiazole-2-thiol was deprotonated in a strongly alkaline aqueous solution utilizing NaOH. Afterwards, the solvent (water) was removed and the product was dried. As a result, the sodium salt of 5-amino-1,3,4-thiadiazole-2-thiol was obtained.

In the second step, the sodium salt was transferred into dimethylformamide (DMF) and 3-chloropropyltrimethoxysilane (dissolved in DMF) was added to form a reaction mixture. The reaction mixture was heated to approximately 100°C under reflux for 15 hours. In the meantime, insoluble sodium chloride precipitated and contaminated the desired product. At least partial removal of sodium chloride by filtration resulted in additional product losses (up to 5%). As a result, a yellow, highly viscous material was obtained.

C) Solubility and stability test:
C-1 Solubility test:
In the solubility test, solubility in diethylene glycol monobutyl ether (DEGBE) and ethylene glycol monobutyl ether (EGBE) as solvents was tested at approximately 22° C. under constant stirring. For this purpose, the azole silane compound of formula (Ia) obtained in Example A), 1) and the reference compound of formula (X) were dissolved in the respective samples (mixtures).

In each solubility test, an amount of the respective compound in a highly viscous state corresponding in each case to a concentration of 50 g/L of the azole silane compound (approximately corresponding to 5% by weight relative to the total weight of the respective test composition) The time "t" required for complete dissolution in each solvent was determined. Each solubility test was run for 30 minutes.

The results are summarized in Table 1 below.

A sample containing a compound of formula (Ia) is a mixture according to the invention, a sample containing a compound of formula (X) is a mixture not according to the invention.

Complete dissolution and clear homogeneous solution were never obtained with the reference compound of formula (X) in EGBE. After 30 minutes, a residue of yellow, highly viscous material was still present, indicating that the compound of formula (X) was not completely solubilized in EGBE. In contrast, complete solubilization was achieved for the compound of formula (Ia) after 10 minutes. A clear, colorless, homogeneous solution was obtained. Furthermore, the presence of contaminating halide ions can be completely excluded.

In DEGBE, complete solubilization of the reference compound took approximately twice as long compared to the compound of formula (Ia). With the azole silane compound of formula (Ia) in DEGBE, a clear, colorless solution was already obtained after 12 minutes. Furthermore, the presence of contaminating halide ions can be completely excluded.

In the case of reference compound (X), the presence of contaminating halide ions cannot be completely excluded.

As a result, the azole silane compounds of formula (I) according to the invention exhibit significantly increased solubility in certain organic solvents (glycol ethers) compared to known azole silane compounds.

C-2 Stability test:
C-2i) Alkaline storage solution:
In a first stability test, the stability of the compounds of formula (Ib) obtained in Examples A), 3) was further investigated in terms of pH dependence.

For that purpose, each of Various stock solutions (according to the invention and not according to the invention) were prepared containing a total amount of compounds of formula (Ib) of 4% by weight. Various pH values were obtained by adding sodium hydroxide or sulfuric acid. Stability was assessed after 1, 7, and 15 days by carefully determining the presence of precipitate. During stability testing, the temperature of each stock solution was 50°C. The results are summarized in Table 2 below.

Storage solutions with pH 4 and 7 are not according to the invention.
In DEGBE, the compound of formula (Ib) is stable at relatively high pH and a concentration of approximately 4% by weight. This is advantageous since in such conditions the compound of formula (I) can still be transported in sufficiently high concentrations to other manufacturing sites.

Starting at an alkaline pH, the precipitation is significantly reduced and disappears completely starting at a pH between 10 and 11. As a result, a clear solution is obtained, which is stable for at least 15 days. Within the pH range below 9-11 (eg 10.4) only slight precipitation is observed, which may be acceptable depending on the further application.

Therefore, a concentration of approximately 4% by weight can be sufficiently stabilized at alkaline pH and in the presence of significant amounts of water-miscible organic solvents. If the total amount of water is relatively small, the respective storage solution is not sufficiently stable at acidic and neutral pH.

C-2ii) Aqueous working solution:
In a second stability test, the stability of the compound of formula (Ib), also obtained in Example A), 3), was investigated at different pH values but at lower concentrations compared to C-2i. .

For that purpose, 250 mL/L of each of the above compounds under entry C-2i, such that the compound of formula (Ib) is present in a total amount of approximately 1% by weight relative to the total weight of the respective use solution. Various use solutions (according to the invention and not according to the invention) were prepared, including a stock solution at pH 11 and 750 mL/L of water. Various pH values were obtained by adding sulfuric acid. Stability was assessed after 14 days by carefully determining the presence of precipitate. During stability testing, the temperature of each stock solution was kept constant at 50°C. The results are summarized in Table 3.

Use solutions with a pH of 4 and 10 are not according to the invention.

Within the pH range of 4.7 to 8.0, no or only minor non-problematic precipitation was observed. Although slight precipitation occurred at pH 8, each working solution was still acceptable.

However, less precipitation is observed within the pH range of 4.8-7.7, and the best results are observed in the pH range of 5.5-7.4, which is a very favorable pH range, and even better in the pH range of 6.5-7.5. This was the result.

Thus, when the solution is aqueous and contains at least 51% by weight water and one or more water-miscible organic solvents, a typical working concentration, e.g. 1% by weight azole silane. Compounds can be sufficiently stabilized at around neutral pH.

Claims (12)

Formula (I)
[In the formula,
X represents NH ₂ , NH(NH ₂ ), NH(NHU), or NHU ,
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents H or C1-C5 alkyl]
azole silane compound. 2. A compound according to claim 1, wherein X represents _NH2 or NH( _NH2 ) . 3. The compound according to claim 1, wherein in U, n is an integer ranging from 1 to 8. Formula (Ia) or (Ib)
[In the formula,
R is independently (CH ₂ -CH ₂ -O) _m -Z;
independently,
m is 0, 1, or 2 ;
Z represents H, _CH3 , _CH2 - _CH3 , ( _CH2 ) ₂ - _CH3 , or ( _CH2 ) ₃ - _CH3 ]
4. A compound according to any one of claims 1 to 3, which is a compound of. (a) one or more than one azole silane compound according to any one of claims 1 to 4 ;
(b) Mixtures containing one or more organic solvents. (a) one or more than one azole silane compound according to any one of claims 1 to 4 ;
(b) water;
(c) An alkaline storage solution containing one or more water-miscible organic solvents, provided that the pH is greater than or equal to 9. In the solution, the total amount of all the azole silane compounds according to any one of claims 1 to 4 together ranges from 0.5% to 15% by weight, based on the total weight of the alkaline storage solution. 7. The storage solution of claim 6 . An aqueous use solution having a pH in the range of 4.8 to 8.0, comprising:
(a) one or more than one azole silane compound according to any one of claims 1 to 4 ;
(b) at least 51% by weight of water, based on the total weight of the working solution;
(c) the total amount of all azole silane compounds according to any one of claims 1 to 4 together in said use solution, comprising one or more water-miscible organic solvents ; is not more than 5% by weight, based on the total weight of the aqueous use solution. Claim 6 or 7 , wherein the one or more water-miscible organic solvents comprise water- miscible organic solvents selected from the group consisting of C1-C4 alcohols, glycol ethers, and mixtures thereof. 9. An alkaline storage solution according to claim 8 , or an aqueous use solution according to claim 8. Formula (I)
[In the formula,
X represents NH ₂ , NH(NH ₂ ), NH(NHU), or NHU ,
Y represents NH, N(NH ₂ ), N(NHU), or S,
U independently represents CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) _n -Si(OR) ₃ and R independently represents (CH ₂ -CH ₂ -O) _m -Z. Yes, independently
n is an integer ranging from 1 to 12;
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl]
A method for synthesizing an azole silane compound, comprising:
(i) Formula (III)
[In the formula,
X represents NH ₂ or NH(NH ₂ ) ,
Y represents NH, N(NH ₂ ), or S]
a step of preparing an azole compound;
(ii) Formula (IV)
[In formula (IV),
R represents (CH ₂ -CH ₂ -O) _m -Z, and independently,
m is 0, 1, 2, 3, or 4;
Z represents C1-C5 alkyl,
n is an integer in the range 1 to 12]
a step of preparing a silane compound;
(iii) reacting said azole compound with said silane compound in a solvent, resulting in a compound as defined above of formula (I);
(iv) Optionally, the compound of formula (I) obtained in step (iii) is hydrolyzed so that at least one of R is m=0 and Z=H (CH ₂ -CH ₂ - O) A synthetic method comprising the step of making _m -Z. 11. The method according to claim 10 , wherein the total molar ratio of compounds of formula (III) to compounds of formula (IV) ranges from 1:0.85 to 1:1.3. 9. Use of the aqueous use solution according to claim 8 as a surface treatment solution.